Mechanism of Ozonolysis. The Initial Ozonide. Lack of Evidence for "Unified Concept" Involving Staudinger Molozonide

Bailey, Philip S.; Thomas, Peter; Fischer, Charles M.; Thompson, James A.

doi:10.1139/v73-193

Cited by 15 publications

(2 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Specifically, 8 reportedly was formed in high yield from ethylidenecyclohexane. However, no 8 could be detected among the products when the reaction was repeated (13,44). Also, the reported synthesis, using this reaction, of the dioxetane of bifluorenylidene (45) could not be repeated in two laboratories (36h 46).…”

Section: Discussionmentioning

confidence: 97%

Preparation and Thermolysis of Some 1,2-Dioxetanes

Kopecky¹,

Filby²,

Mumford³

et al. 1975

Can. J. Chem.

142

View full text Add to dashboard Cite

DING. Can. J. Chem. 53,1103 (1975. Treatment of the bromohydroperoxides of 2-methyl-2-butene and ethylidenecyclohexane with cold methanolic base produces trimethyl-and 4-methyl-3,3-pentamethylene-1 ,2-dioxetane, 3 and 8. Under these conditions the bromo-and iodohydroperoxides of 2,3-dimethyl-2-butene A, 1,2-dimethylcyclohexene B, and AgJO-octalin C are converted rapidly to the corresponding allylic hydroperoxides. The reaction in methylene chloride between silver ion and the bromoand iodohydroperoxides of A and the iodohydroperoxides of B and C produces the corresponding dioxetanes in 20-30% yield: tetramethyl-1,Zdioxetane 11, 3,4-dimethyl-3,Cbutano-1,2-dioxetane 15, and 3,4:3,4-dibutano-1,2-dioxetane 23. About 50% of the corresponding allylic hydroperoxides also are formed as are pinacolone, -15%, l-acetyl-l-methylcyclopentane, ~2 0 % , and Ag.lO-octalin, -l%, from the appropriate halohydroperoxides.All the dioxetanes are yellow, thermolyze to give only carbonyl cleavage products, and are luminescent. Reduction of 3 with bisulfite ion produced trimethyloxacyclopropane and with iodide ion 2-methyl-2,3-butanediol. Reduction of 8,11,15, and 23 with lithium aluminum hydride at -78" gave good yields of the corresponding diols. Treatment with triphenylphosphine of 11 gave tetramethyloxacyclopropane, of 15, a 1 : 3 ratio of 2-methylene-1-methylcyclohexanol and 2,3-dimethylcyclohexen-3-01, and of 23, 10-hydroxy-A'~9-octalin.Activation parameters for thermolysis of the dioxetanes are (dioxetane, E,, kcal/mol, AS*, e.u.)3, 23.5 a 0.5, -5 f 2; 11, 25.8 f 0.5, -2 + 2; 15, 25.7 a 0.7, 2 f 2; 23, 22.7 f 0.9, -3 f 3. 3Holder of a Canadian Mortgage and Housing Corporation Fellowship, 1970 and a National Research Council of Canada Scholarship, 1971 4Holder of a National Research Council of Canada Scholarship, 1970Scholarship, -1973 Can. J. 53, 1975 20-30%: t6tramethyldioxetanne-1,2, 11, dimethyl-3,4 butano-3,4 dioxktanne-1,2, 15, et di-I butano-3,4:3,4 dioxetanne-1,2, 23. Dans ces reactions, il se forme environ 50% des hydroperoxydes allyliques correspondants et suivant les hydroperoxydes utilises de la pinacolone, 15% (approx), de I'acktyl-1 methyl-1 cyclopentane, 20% (approx), et de la A9*10-octaline, 1% (approx). Tous les dioxetannes sont des composks jaunes et luminescents, dont la thermolyse ne donne que les produits de fission carbonylique. La reduction de 3 avec le bisulphite donne le trim~thyloxacyclopropane alors que les ions iodures conduisent au methyl-2 butanediol-2,3. La reduction de 8,11,15 et 23 avec I'hydrure de lithium et aluminium ii -78" donne des bons rendements des diols correspondants. Le traitement de 11 avec de la triph6nylphosphine transforme 11 en t6tram6thyloxacyclopropane; 15 en methylene-2 methyl-1 cyclohexanol et en dimethyl-2,3 cyclohex8n-3-01 dans le rapport 1 : 3; et 23 en hydroxy-10 A1.9-octaline.Les parametres d'activation pour la thermolyse des dioxetannes sont (dioxktanne, E., kcal mol-l,AS* ~aldeg-~mol-');3,23.5 + 0.5, -5 + 2;11,25.8 + 0.5, -2 + 2;15,25.7 + 0.7, 2 + 2; 23, 22.7 + 0.9...

show abstract